Microporous structure of an organic metal complex

ABSTRACT

A porous structure includes an organic metal complex represented by the following general formula (1): 
 
M·L(A,B) 3   (1) 
(where M represents a metal atom; L (A, B) represents a ligand constituted of A and B; and A and B respectively represent cyclic groups which may have or may not have one or more substituents).

TECHNICAL FIELD

The present invention relates to a technical field of a zeolite which isa porous body, and more particularly to a microporous structure (organiczeolite) made of an organic metal complex.

BACKGROUND ART

In recent years, various porous materials have attracted attention. Theporous body is classified into three types: a microporous body having apore size of 2 nm or less; a mesoporous body having a pore size of 2 to50 nm; and a macroporous body having a pore size of 50 nm or more. Azeolite belonging to the microporous body is a porous crystallinealuminosilicate formed from a three-dimensional mesh structure of a TO₄tetrahedral body (where T represents silicon or aluminum). Further,recently, an organic zeolite having pores formed by a network of anorganic compound containing a metal has attracted attention. The organiczeolite generally has a lower density than that of the zeolite.Accordingly, the organic zeolite is a lightweight material and can bereadily recovered or reused using a solvent. Thus, as a high-performancematerial substitutive for the zeolite, the organic zeolite has beenhighly expected as being capable of applying to a gas storage material,a gas sensor, or the like.

DISCLOSURE OF THE INVENTION

The present invention provides a microporous structure including anorganic metal complex molecule, containing a metal atom in its center.

More specifically, the present invention provides a porous structurecomprising an organic metal complex represented by the following generalformula (1):M·L(A,B)₃  (1)(where M represents a metal atom; L (A, B) represents a ligand comprisedof A and B; and A and B respectively represent cyclic groups which mayhave or may not have one or more substituents).

Further, the present invention provides a porous structure as mentionedabove, in which the general formula (1) is represented by the generalformula (2):

(where M represents a metal atom; A and B respectively represent cyclicgroups which may have or may not have one or more substituents, in whichthe substituent is a halogen atom, a nitro group, a trialkylsilyl group(in which alkyl groups are linear or branched alkyl groups having 1 to 8carbon atom(s) independently of one another), or a linear or branchedalkyl group having 1 to 20 carbon atom(s) (in which one methylene groupor two or more methylene groups not adjacent to each other in the alkylgroup may be substituted for —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or—C≡C—, and a hydrogen atom in the alkyl group may be substituted for afluorine atom)).

The present invention provides a porous structure as mentioned above,characterized in that the porous structure has a three-dimensionalstructure of a facial isomer represented as the following structure.

The present invention provides a porous structure as mentioned above, inwhich at least one of the cyclic groups A and B bonded to the metal atomM in the general formula (1) is one selected from the group consistingof pyridine, pyrimidine, pyrazoline, pyrrole, pyrazole, quinoline,isoquinoline, imidazole, quinone, benzoazepin, catechol, phenol, phenyl,naphthyl, thienyl, benzothienyl, quinolyl, phenothiazine, benzothiazole,benzoxazole, and benzoimidazole.

The present invention provides a porous structure as mentioned above, inwhich the metal atom M in the general formula (1) is Ir.

The present invention provides a method of manufacturing a porousstructure, characterized by including: a step of dissolving an organicmetal complex represented by the general formula (1) in a solvent toobtain a solution; a step of precipitating the organic metal complexfrom the solution to form the porous structure; and a step of removingthe solvent in the porous structure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing a three-dimensional structure of iridium(III) tris(1-phenylisoquinoline) given by a single crystal X-raystructure analysis.

FIG. 2 is a diagram showing an arrangement of iridium (III)tris(1-phenylisoquinoline) in a unit lattice.

FIG. 3 is a diagram showing an arrangement of iridium (III)tris(1-phenylisoquinoline) in a unit lattice.

FIG. 4 is a diagram showing an arrangement of iridium (III)tris(1-phenylisoquinoline) in arranged unit lattices.

FIG. 5 is a diagram showing a powder X-ray diffraction pattern ofiridium (III) tris(1-phenylisoquinoline).

FIG. 6 is a diagram showing a powder X-ray diffraction pattern ofiridium (III) tris(1-phenylisoquinoline) at room temperature and at ahigh temperature.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail hereinafter.

A synthesis procedure of an organic metal complex compound representedby the above general formula (2) and used in the present invention isshown below using an iridium complex compound as an example.Synthesis of a ligand L (reference document: Kevin R. et al., Org.Lett., 1999, 1, 553-556):

Synthesis of an Iridium Ligand Compound:

The obtained compound was dissolved in a solvent and then precipitated,to yield a porous structure. In examples, a single crystal X-raydiffraction was conducted using RINT-RAPID, manufactured by Rigaku DenkiCo. A pore size was obtained from the crystal structure analysis andpowder X-ray diffraction determination was conducted using X′ Pert-PRO,manufactured by Philips Co.

EXAMPLE

An organic metal complex compound represented by the general formula (1)where A represents a phenyl group and B represents an isoquinolinegroup, was synthesized in the following procedure.

69.3 g of isoquinoline N-oxide (448 mmole) available from Tokyo KaseiCo. and 225 ml of chloroform were introduced into a 1 L-three-neck flaskto dissolve therein. Then, 219.6 g (1432 mmole) of phosphorousoxychloride was slowly dropped therein and stirred under ice-coolingwhile maintaining the inner temperature at 15 to 20° C. Thereafter, thetemperature was raised, and the mixture was stirred under reflux for 3hours. The reaction product was left to cool to room temperature,followed by pouring the resultant into an ice water. The mixture wasextracted with ethyl acetate, an organic layer was washed with watertill it showed neutral pH, and then the solvent was removed underreduced pressure. The residue was purified using silica gel columnchromatography (eluent: chloroform/hexane: 5/1), to yield 35.5 g of awhite crystal of 1-chloroisoquinoline (44.9% yield).

3.04 g of phenylboronic acid (24.9 mmole) and 4.09 g of1-chloroisoquinoline (25.0 mmole), 25 ml of toluene, 12.5 ml of ethanol,and 25 ml of 2M-sodium carbonate aqueous solution were introduced into a100 ml-three-neck flask. With stirring at room temperature under anitrogen gas flow, 0.98 g (0.85 mmole) of tetrakis-(triphenylphosphine)palladium (0) was added to the mixture. Thereafter, the resultant wasstirred under reflux under a nitrogen gas flow for 8 hours. After thereaction, the reaction product was cooled, and then added with ice waterand toluene to extract the organic layer. The organic layer was washedwith saline and dried with magnesium sulfate, and then the solvent wasremoved under reduced pressure. The residue was purified using silicagel column chromatography (eluent: chloroform/methanol: 10/1), to yield2.20 g of 1-phenylisoquinoline (43.0%

50 ml of glycerol was introduced into a 100 ml-four-neck flask, and thenstirred and heated at 130 to 140° C. for 2 hours with bubbling anitrogen gas. The glycerol was left to cool to 100° C., and then addedwith 1.03 g (5.02 mmole) of 1-phenylisoquinoline and 0.50 g (1.02 mmole)of iridium (III) acetylacetonate. The reaction mixture was stirred andheated for 7 hours at around 210° C. under the nitrogen gas flow. Afterbeing left to cool to room temperature, the reaction product was addedto 300 ml of 1N-hydrochloric acid, and the precipitate was filtrated andthen washed with water. The precipitate was purified using silica gelcolumn chromatography with chloroform used as an eluent, to yield 0.22 gof a red powder of iridium (III) tris(1-phenylisoquinoline) (26.8%yield).

For preparing a single crystal, 1.5 mg of purified iridium (III)tris(1-phenylisoquinoline) powder was first dissolved in 15 ml ofchloroform at room temperature. Then, ethanol was poured tillsaturation, and the solution was filtrated to obtain a saturatedsolution. The solvent in the saturated solution was evaporated gentlyunder an isothermal condition, to yield a single crystal in the form ofred needle crystal. A sample obtained by drying at 100° C. for 3 hourswas used for a single crystal X-ray structure analysis. The singlecrystal X-ray structure analysis was conducted as follows: the singlecrystal in liquid paraffin was scooped up with a sample fixing element,and measured while being cooled to 100 K with cooled nitrogen. Thecrystal structure data obtained by the single crystal X-ray structureanalysis is shown in Tables 1 to 3. Parameters shown in the tables arerepresented in units generally adopted by those skilled in the art.Those units are described in more detail in the following document:International Tables for X-ray Crystallography, Vol. IV, pp. 55, 99,149. TABLE 1 Single crystal X-ray structure analysis of iridium (III)tris(1-phenylisoquinoline) (crystal parameters) Crystal size(mm) 0.05 ×0.05 × 0.05 Unit lattice size (Å) a = 16.4781(7) Å b = 16.4781(7) Å c =15.9151(8) Å α = 90° β = 90° γ = 120° V = 3742.4(3) Å³ Space group P-3c1Molecular/Unit lattice Trigonal system 4 Calculated density(g/cm³) 1.429

TABLE 2 Atomic coordinates and isotropic temperature factor (Å²) Atom xy z Beq Ir(1) 0.6667   0.3333    0.38699(2)  1.109(5) N(1) 0.6162(4)0.2081(3) 0.4593(3)  1.26(9) C(1) 0.5589(4) 0.1861(4) 0.5284(4) 1.4(1)C(2) 0.5388(4) 0.1127(4) 0.5793(4) 1.5(1) C(3) 0.5867(4) 0.0615(5)0.5672(4) 1.7(1) C(4) 0.5773(5) −0.0095(5)  0.6248(4) 2.0(1) C(5)0.6304(5) −0.0508(5)  0.6155(4) 2.4(1) C(6) 0.6963(5) −0.0234(5) 0.5511(5) 2.2(1) C(7) 0.7062(5) 0.0439(5) 0.4929(4) 1.9(1) C(8)0.6480(4) 0.0847(4) 0.4976(4) 1.7(1) C(9) 0.6527(4) 0.1541(4) 0.4389(4)1.4(1) C(10) 0.7001(4) 0.1773(4) 0.3560(4) 1.4(1) C(11) 0.7189(4)0.1154(4) 0.3105(4) 1.5(1) C(12) 0.7640(5) 0.1433(5) 0.2334(4) 1.7(1)C(13) 0.7895(5) 0.2306(5) 0.2007(3) 1.6(1) C(14) 0.7650(4) 0.2898(4)0.2428(4) 1.4(1) C(15) 0.7178(5) 0.2643(5) 0.3219(4) 1.6(1) H(1)0.5330(4) 0.2247(4) 0.5414(4) 1.6(2) H(2) 0.4932(4) 0.0953(4) 0.6224(4)1.6(2) H(3) 0.5339(5) −0.0276(5)  0.6698(4) 2.3(2) H(4) 0.6222(5)−0.0987(5)  0.6536(4) 2.8(2) H(5) 0.7350(5) −0.0508(5)  0.5472(5) 2.8(2)H(6) 0.7518(5) 0.0628(5) 0.4496(4) 2.3(2) H(7) 0.7016(4) 0.0556(4)0.3331(4) 1.7(2) H(8) 0.7764(5) 0.1014(5) 0.2025(4) 2.1(2) H(9)0.8252(5) 0.2514(5) 0.1504(3) 1.9(2) H(10) 0.7788(4) 0.3479(4) 0.2182(4)1.7(1)

TABLE 3 Anisotropic temperature factor (Å²) Atom U11 U22 U33 U12 U13 U23Ir(1)  0.0158(1)  0.0158(1)  0.0106(1)  0.00790(6) 0.0000  0.0000  N(1)0.017(3) 0.016(2) 0.015(2) 0.009(2) −0.004(2)  −0.006(2)  C(1) 0.019(3)0.016(3) 0.016(3) 0.007(2) −0.002(2)  −0.002(2)  C(2) 0.016(3) 0.019(3)0.016(2) 0.005(2) 0.000(2) −0.001(2)  C(3) 0.016(3) 0.021(3) 0.024(3)0.006(3) −0.001(3)  0.001(3) C(4) 0.027(3) 0.024(3) 0.022(3) 0.011(3)0.004(3) 0.004(3) C(5) 0.034(4) 0.024(3) 0.029(3) 0.011(3) 0.001(3)0.004(3) C(6) 0.038(4) 0.023(3) 0.029(3) 0.019(3) −0.003(3)  0.003(3)C(7) 0.022(3) 0.026(3) 0.024(3) 0.012(3) 0.001(3) 0.001(3) C(8) 0.018(3)0.017(3) 0.022(3) 0.003(2) −0.002(3)  0.004(3) C(9) 0.020(3) 0.016(3)0.017(3) 0.007(2) −0.004(2)  0.001(2) C(10) 0.019(3) 0.020(3) 0.013(2)0.008(3) 0.002(2) −0.000(2)  C(11) 0.020(3) 0.016(3) 0.018(3) 0.008(2)−0.003(2)  −0.003(2)  C(12) 0.024(3) 0.024(3) 0.019(3) 0.014(3) 0.002(3)−0.005(3)  C(13) 0.021(4) 0.025(4) 0.014(2) 0.011(3) 0.002(3) 0.000(3)C(14) 0.020(3) 0.021(3) 0.012(2) 0.010(2) −0.005(2)  −0.002(2)  C(15)0.020(4) 0.026(4) 0.019(2) 0.014(3) 0.000(3) 0.003(3)

FIG. 1 to FIG. 4 are diagrams where the atomic coordinates obtained bythe X-ray structure analysis shown in Tables 1 to 3 are plotted. Asapparent from FIG. 1, iridium (III) tris(1-phenylisoquinoline) was afacial isomer. FIG. 4 is a diagram showing a structure of the unitlattices arranged. As apparent from FIG. 4, pore structures existedregulatively in the crystal structure. The pore size was approximately 8Å, and the calculated porosity was about 21%.

The red powder of iridium (III) tris(1-phenylisoquinoline) dried at 100°C. for 3 hours was subjected to the determination by the powder X-raydiffraction method. The powder X-ray diffraction data is shown in FIG.5. It was confirmed from the obtained diffraction peak that the crystalstructure of the powder was similar to that of the single crystal. Toobtain the knowledge about a thermal stability of iridium (III)tris(1-phenylisoquinoline), the red powder of iridium (III)tris(1-phenylisoquinoline) dried for 3 hours was subjected to adetermination of in-situ observation at around 200° C. by ahigh-temperature X-ray diffraction method. FIG. 6 shows powder X-raydiffraction data obtained at room temperature and 200° C. As shown inFIG. 6, the structure was kept stable even at 200° C.

The substance of the above zeolite structure was considered to havefunctions such as selective capture and permeation of substances,thereby achieving functions of a separation material, a storagematerial, etc. Moreover, by arranging specific substances in pores ofthe zeolite, it is possible to develop a new optical/magnetic/electronicmaterial, which expresses specific optical/magnetic/electroniccharacteristics.

1. A porous structure comprising an organic metal complex represented bythe following general formula (1):M·L(A,B)₃  (1) (where M represents a metal atom; L (A, B) represents aligand comprised of A and B; and A and B respectively represent cyclicgroups which may have or may not have one or more substituents).
 2. Aporous structure according to claim 1, wherein the general formula (1)is represented by the general formula (2):

(where M represents a metal atom; A and B respectively represent cyclicgroups which may have or may not have one or more substituents, in whichthe substituent is a halogen atom, a nitro group, a trialkylsilyl group(in which alkyl groups are linear or branched alkyl groups having 1 to 8carbon atom(s) independently of one another), or a linear or branchedalkyl group having 1 to 20 carbon atom(s) (in which one methylene groupor two or more methylene groups not adjacent to each other in the alkylgroup may be substituted for —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or—C≡C—, and a hydrogen atom in the alkyl group may be substituted for afluorine atom)).
 3. A porous structure according to claim 1, wherein theporous structure has a three-dimensional structure of a facial isomerrepresented as the following structure.


4. A porous structure according to claim 1, wherein at least one of thecyclic groups A and B bonded to the metal atom M in the general formula(1) is one selected from the group consisting of pyridine, pyrimidine,pyrazoline, pyrrole, pyrazole, quinoline, isoquinoline, imidazole,quinone, benzoazepin, catechol, phenol, phenyl, naphthyl, thienyl,benzothienyl, quinolyl, phenothiazine, benzothiazole, benzoxazole, andbenzoimidazole.
 5. A porous structure according to claim 1, wherein themetal atom M in the general formula (1) is Ir.
 6. A method ofmanufacturing a porous structure, characterized by comprising: a step ofdissolving an organic metal complex represented by the general formula(1) in a solvent to obtain a solution; a step of precipitating theorganic metal complex from the solution to form the porous structure;and a step of removing the solvent in the porous structure:M·L(A,B)₃  (1) (where M represents a metal atom; L (A, B) represents aligand comprised of A and B; and A and B respectively represent cyclicgroups which may have or may not have one or more substituents).